Metallocene compounds

ABSTRACT

In accordance with the present invention there is provided a cyclopentadienyl-type ligand represented by the formula ZA, wherein Z is a cyclopentadienyl-type group, wherein A is --YPR 2 , --YNR 2 , or --NR 2 , wherein Y is an alkylene group containing 1 to 24 carbon atoms, wherein each R is individually selected from alkyl groups containing 1 to 20 carbon atoms. Another aspect of the invention is to provide a metallocene represented by the formula ZAMX 3 , wherein Z and A are as described above, M is a Group IVB or VB transition metal, and X is a halide. Other aspects of the present invention include catalyst systems comprising the metallocenes and an organoaluminoxane, processes for preparing the above defined ligands, metallocenes and catalyst systems, and polymerization processes employing the catalyst systems.

This is a divisional of copending application Ser. No. 08/303,982, filedSep. 9, 1994 now abandoned.

The present invention relates to the preparation of heterodifunctionalcyclopentadienyl-type ligands and metallocenes.

BACKGROUND OF THE INVENTION

Cyclopentadienyl-type ligands have found a number of uses in the past.As used herein, the term cyclopentadienyl-type ligands includes ligandscontaining a cyclopentadienyl-type group. Cyclopentadienyl-type groupsas used herein contain a cyclopentadienyl functionality and includeunsubstituted cyclopentadienyl, substituted cyclopentadienyl,unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, andsubstituted fluorenyl groups. Such ligands have utility in thepreparation of metallocenes useful for the polymerization of olefins.

Other applications for metallocenes include asymmetric hydrogenation,alkene epoxidation, alkene isomerization, ketone reduction, and asstoichiometric reagents for stereoselective cobalt-mediated reactions,allyltitanium addition reactions with aldehydes, and the highlyselective formation of allylic amines.

It would therefore be desirable to produce a variety of novel ligandsfrom readily available materials employing a simple and economicalprocess.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an economical andsimple processes for preparing new cyclopentadienyl-type ligands.

Another object of the present invention is to provide a variety ofcyclopentadienyl-type ligands useful in preparing metallocenes.

Another object of the present invention is to provide variousmetallocenes useful in the polymerization of olefins.

Another object of the present invention is to provide processes forpreparing new metallocenes.

Another object of the present invention is to provide catalyst systemscapable of polymerizing olefins.

Another object of the present invention is to provide processes forpreparing catalyst systems.

Another object of the present invention is to provide olefinpolymerization processes employing the catalyst systems.

In accordance with the present invention there is providedcyclopentadienyl-type ligands represented by the formula ZA, wherein Zis a cyclopentadienyl-type group and wherein A is --YPR₂, --YNR₂, or--NR₂ wherein Y is an alkenyl or substituted alkenyl group containing 1to 24 carbon atoms and wherein each R is individually selected fromalkyl groups containing 1 to 20 carbon atoms. Another aspect of theinvention is to provide metallocenes represented by the formula ZAMX₃,wherein Z and A are as described above, M is a Group IVB or VBtransition metal, and X is a halide. Other aspects of the presentinvention include catalyst systems comprising the metallocenes and anorganoaluminoxane, processes for preparing the above defined ligands,metallocenes and catalyst systems, and polymerization processesemploying the catalyst systems.

DETAILED DESCRIPTION OF THE INVENTION

The cyclopentadienyl-type ligands of the present invention arerepresented by the formula ZA, wherein Z is a cyclopentadienyl-typegroup and A is --YPR₂, --YNR₂, or --NR₂, wherein Y is an alkylene groupcontaining 1 to 24 carbon atoms, wherein each R is individually selectedfrom alkyl groups containing 1 to 20 carbon atoms, preferably 1 to 10carbon atoms, more preferably 1 to 5 carbon atoms, and most preferablythe R groups are methyl or ethyl. Preferably Y contains 1 to 20 carbonatoms, more preferably 1 to 16 carbon atoms, and most preferably Y is anunsubstituted or substituted methylene or ethylene group. Some examplesof Y include methylene, ethylene, dimethylmethylene, dimethylethylene,phenylethylene, butylethylene, diphenylethylene, propylene, andbutylene. Some examples of R include methyl, ethyl, propyl, isopropyl,butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl,octyl, nonyl, decyl, cetyl, 2-ethylhexyl. Excellent results have beenobtained when R is methyl and those compounds are preferred. In thefollowing examples Me is methyl, Et is ethyl, Ph is phenyl, and t-Bu istert-butyl. Typical examples of A include --CH₂ PMe₂, --CH₂ CH₂ PMe₂,--CMe₂ PMe₂, --CMe₂ CH₂ PMe₂, --CPhHCH₂ PMe₂, --CPh₂ CH₂ PMe₂,--C(t-Bu)HCH₂ PMe₂, --CH₂ PMe₂, --CH₂ CH₂ PMe₂, --CMe₂ PMe₂, --CMe₂ CH₂PMe₂, --CPhHCH₂ PMe₂, --CPh₂ CH₂ PMe₂, --C(t-Bu)HCH₂ PMe₂, --CH₂ PEt₂,--CH₂ CH₂ PEt₂, --CMe₂ PEt₂, --CMe₂ CH₂ PEt₂, --CPhHCH₂ PEt₂, --CPh₂ CH₂PEt₂, --C(t-Bu)HCH₂ PEt₂, --CH₂ PEt₂, --CH₂ CH₂ PEt₂, --CMe2PEt₂, --CMe₂CH₂ PEt₂, --CPhHCH₂ PEt₂, --CPh₂ CH₂ PEt₂, --C(t-Bu) HCH₂ PEt₂, --CH₂NMe₂, --CH₂ CH₂ NMe₂, --CMe₂ NMe₂, --CMe₂ CH₂ NMe₂, --CPhHCH₂ NMe₂,--CPh₂ CH₂ NMe₂, --C(t-Bu)HCH₂ NMe₂, --CH₂ NMe₂, --CH₂ CH₂ NMe₂, --CMe₂NMe₂, --CMe₂ CH₂ NMe₂, --CPhHCH₂ NMe₂, --CPh₂ CH₂ NMe₂, --C(t-Bu)HCH₂NMe₂, --CH₂ NEt₂, --CH₂ CH₂ NEt₂, --CMe₂ NEt₂, --CMe₂ CH₂ NEt₂,--CPhHCH₂ NEt₂, --CPh₂ CH₂ NEt₂, --C(t-Bu)HCH₂ NEt₂, --CH₂ NEt₂, --CH₂CH₂ NEt₂, --CMe₂ NEt₂, --CMe2CH₂ NEt₂, --CPhHCH₂ NEt₂, --CPh₂ CH₂ NEt₂,--C(t-Bu)HCH₂ NEt₂, --NMe₂, and --NEt₂.

As noted above, cyclopentadienyl-type group as used herein is a groupcontaining a cyclopentadienyl functionality and is an unsubstitutedcyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,substituted indenyl, unsubstituted fluorenyl, or substituted fluorenylgroup. The substituents on the cyclopentadienyl-type group can includehydrocarbyl groups containing 1 to 12 carbon atoms, alkoxy groupscontaining 1 to 12 carbon atoms, trialkylsilyl groups where each alkylcontains 1 to 12 carbon atoms, alkyl halide groups where the alkylcontains 1 to 12 carbon atoms, or halide. Preferably the substituentscontaining alkyl groups contain 1 to 10 carbon atoms, more preferably 1to 6 carbon atoms. Some examples of substituents include methyl, ethyl,propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl,heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl,phenyl, chloride, bromide, and iodide.

Examples of typical cyclopentadienyl-type ligands include

[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadiene,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadiene,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadiene,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadiene,

[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadiene,

[1-phenyl-2-(dimethylphosphino)ethyl]indene,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]indene,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]indene,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indene,

[1-tert-butyl-2-(dimethylphosphino)ethyl]indene,

9-(trimethylsilyl)-9-(1-(2-dimethylphosphino)ethyl)fluorene,

9-(1-(2-dimethylphosphino)ethyl)fluorene,

[(dimethylamino)methyl)]cyclopentadiene,

[(diethylamino)methyl)]cyclopentadiene,

[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadiene,

[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadiene,

[(dimethylamino)(phenyl)methyl)]cyclopentadiene,

[(diethylamino)(phenyl)methyl)]cyclopentadiene,

[1-phenyl-2-(diethylamino)ethyl]cyclopentadiene,

[1-phenyl-2-(dimethylamino)ethyl)cyclopentadiene,

[1-phenyl-2-(dimethylamino)ethyl]cyclopentadiene,

1,1-dimethyl-2-(dimethylamino)ethyl]cyclopentadiene,

[1,1-diphenyl-2-(dimethylamino)ethyl]cyclopentadiene,

[1-methyl-1-phenyl-2-(dimethylamino)ethyl]cyclopentadiene,

[1-tert-butyl-2-(dimethylamino)ethyl]cyclopentadiene,

[1-phenyl-2-(dimethylamino)ethyl]indene,

[1,1-dimethyl-2-(dimethylamino)ethyl]indene,

[1,1-diphenyl-2-(dimethylamino)ethyl]indene,

[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indene,

[1-tert-butyl-2-(dimethylamino)ethyl]indene,

9-(dimethylamino)methyl)fluorene, 9-(1-(2-dimethylamino)ethyl)fluorene,

9-(trimethylsilyl)-9-(dimethylamino)methyl)fluorene, and

9-(trimethyl silyl)-9-(1-(2-dimethylamino)ethyl)fluorene.

One method for preparing the cyclopentadienyl-type ligands, Method I,involves reacting fulvene compounds with a nucleophile, wherein thenucleophile is represented by the formula JA, wherein J is an alkalimetal, preferably lithium, and wherein A is as described above.

The fulvene compound is represented by the general formula ##STR1##wherein each R' and R" is individually selected from the groupconsisting of alkyl, aryl, alkenyl, and alkoxy groups containing 1 to 20carbon atoms, preferably 1 to 10 carbon atoms, halogen, and hydrogen;and wherein n is 1 to 4. Some examples of R' and R" include methyl,ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, tert-butyl, amyl,isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, cetyl,2-ethylhexyl, phenyl, and phenylmethyl.

Examples of typical fulvene compounds include 6-methylfulvene,6-ethylfulvene, 6-isopropylfulvene, 6-butylfulvene, 6-tert-butylfulvene,6-octylfulvene, 1,6-dimethylfulvene, 1,2,6-trimethylfulvene,1,2,3,6-tetramethylfulvene,1,2,3,4,6-pentamethylfulvene.6,6-dimethylfulvene,3,6,6-trimethylfulvene, 6,6-diethylfulvene, 6,6-diphenylfulvene,6-ethyl-6-methylfulvene, 6-isopropyl-6-methylfulvene,6,6-dibutylfulvene, 6,6-dioctylfulvene, 6-methyl-6-octylfulvene,6-methyl-6-phenyl, 1,6,6-trimethylfulvene, 1,2,6,6-tetramethylfulvene,1,2,3,6,6-pentamethylfulvene, and 1,2,3,4,6,6-hexamethylfulvene. Of thefulvene compounds, 6-methylfulvene, 6-phenylfulvene, 6-methyl-6-phenyl,6-tert-butylfulvene, 6,6-dimethylfulvene, and 6,6-diphenylfulvene arepreferred because they produce excellent results and are readilyavailable.

The fulvene compounds can be prepared by any method known in the art.One such method is disclosed in J. Org. Chem., Vol. 49, No. 11, pp.1849-53, 1984, the disclosure of which is incorporated herein byreference. Many such compounds are commercially available.

When reacting the fulvene compound and the nucleophile in Method I,generally the nucleophile compound will be present in an amount in therange of from about 0.1 mole to about 20 moles per mole of fulvenecompound, preferably from 0.2 mole to about 10 moles per mole, and morepreferably from 0.5 mole to 5 moles per mole of fulvene compound.

The reaction conditions for reacting the fulvene compound and thenucleophile in Method I are generally in the range of from about -100°C. to about 150° C., preferably from about -100° C. to about 125° C.,and more preferably from -100° C. to about 100° C.

Generally a diluent is employed in Method I when reacting the fulvenecompound and the nucleophile. Typical diluents include polar diluentssuch as for example tetrahydrofuran, or nonpolar diluents such asalkanes, cycloalkanes, aromatic hydrocarbons, and non-cyclic ethers.Some specific examples include toluene, heptane, hexane, anddiethylether.

Another method for preparing the inventive cyclopentadienyl-typeligands, Method II, involves reacting a halocyclopentadienyl-typecompound and the nucleophile JA, described above, wherein thehalocyclopentadienyl-type compound is represented by the formula ZCH₂ X'wherein Z is a cyclopentadienyl-type group as described above and X' isa halide, preferably bromine or chlorine. The method has been founduseful in preparing cyclopentadienyl-type ligands containing anunsubstituted or substituted fluorenyl group.

When reacting the halocyclopentadienyl-type compound and the nucleophilein Method II, generally the nucleophile compound will be present in anamount in the range of from about 0.1 mole to about 20 moles per mole ofhalocyclopentadienyl-type compound, preferably from 0.2 mole to about 10moles per mole, and more preferably from 0.5 mole to 5 moles per mole ofhalocyclopentadienyl-type compound.

The reaction conditions for reacting the fulvene compound and thenucleophile in Method II are generally in the range of from about -100°C. to about 150° C., preferably from about -100° C. to about 125° C.,and more preferably from -100° C. to about 100° C.

Generally a diluent is employed in Method II when reacting thehalocyclopentadienyl-type compound and the nucleophile. Typical diluentsinclude those described above, such as polar diluents such as forexample tetrahydrofuran, or nonpolar diluents such as alkanes,cycloalkanes, aromatic hydrocarbons, and non-cyclic ethers. Somespecific examples include toluene, heptane, hexane, and diethylether.Good results have been obtained with tetrahydrofuran and it ispreferred.

Another method for preparing the inventive cyclopentadienyl-typeligands, Method III, involves (1) reacting a halosilane with an alkalimetal salt of a cyclopentadienyl-type compound to form asilylcyclopentadienyl-type compound, (2) reacting thesilylcyclopentadienyl-type compound with an alkali metal alkyl andmethylene dichloride, to produce a chloromethylatedsilylcyclopentadienyl-type compound, and then (3) reacting thechloromethylated silylcyclopentadienyl-type compound with the abovedefined nucleophile, JA, to produce the cyclopentadienyl-type ligand.This method has been found especially useful in preparingcyclopentadienyl-type ligands containing a fluorenyl group.Silylfluorene compounds can be prepared by any method known such asdisclosed in J. Am. Chem. Soc. 72 (1950) 1688, H. Gilman et al. thedisclosure of which is herein incorporated by reference.

The halosilane compound employed in Method III is represented by theformula X"Si(R¹)₃, wherein X" is a halide and wherein each R¹ isindividually an alkyl group or hydrogen, wherein the alkyl groupcontains 1 to 20 carbon atoms, preferably 1 to 10, and more preferably 1to 5 carbon atoms. Typical examples of R¹ include methyl, ethyl, propyl,isopropyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl,cyclohexyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl. Excellentresults have been obtained with chlorotrimethylsilane and it ispreferred.

Typically the alkali metal salts of cyclopentadienyl-type compoundsemployed in Method III can be prepared by dissolving acyclopentadienyl-type compound in a suitable liquid diluent and thenadding an alkali metal compound, such as an alkali metal alkyl.Techniques of forming such salts are known in the art. The alkali metalalkyls employed in preparing the alkali metal salt of thecyclopentadienyl-type compound can include any alkali metal alkylscapable of forming a suitable alkali metal salt. Typically the alkalimetal alkyls would be selected from the alkyls of sodium, potassium, andlithium and the alkyl group would have 1 to 8, preferably 1 to 6 carbonatoms. The preferred alkali metal alkyls are lithium alkyls. Due toavailability and efficacy, butyllithium is especially preferred. Inpreparing the alkali metal salt of the cyclopentadienyl-type compound,the amount of alkali metal alkyl employed is generally in the range offrom about 0.5 mole to about 50 moles per mole of cyclopentadienyl-typecompound, preferably 0.5 mole to 20 moles per mole ofcyclopentadienyl-type compound.

When reacting the halosilane and the alkali metal salt of thecyclopentadienyl-type compound in step (1) of Method III, the halosilaneis generally present in an amount in the range of from about 0.1 mole toabout 20 moles per mole of cyclopentadienyl-type compound, preferablyfrom 0.2 mole to about 10 moles per mole, and more preferably from 0.5mole to 5 moles per mole of cyclopentadienyl-type compound.

When reacting the silylcyclopentadienyl-type compound, the alkali metalalkyl, and methylene dichloride in step of (2) Method III, the alkalimetal alkyl and methylene dichloride are generally each present in anamount in the range of from about 0.1 mole to about 20 moles per mole ofsilylcyclopentadienyl-type compound, preferably from 0.2 mole to about10 moles per mole, and more preferably from 0.5 mole to 5 moles per moleof silylcyclopentadienyl-type compound.

When reacting the chloromethylated silylcyclopentadienyl-type compoundand the nucleophile in step (3) of Method III, the nucleophile isgenerally present in an amount in the range of from about 0.1 mole toabout 20 moles per mole of chloromethylated silylcyclopentadienyl-typecompound, preferably from 0.2 mole to about 10 moles per mole, and morepreferably from 0.5 mole to 5 moles per mole of chloromethylatedsilylcyclopentadienyl-type compound.

Generally a diluent is employed when conducting the above describedsteps of Method III. Typical diluents include those described above suchas for example polar diluents such as tetrahydrofuran, or nonpolardiluents such as alkanes, cycloalkanes, aromatic hydrocarbons, andnon-cyclic ethers. Some specific examples include benzene, toluene,heptane, hexane, cyclohexane, and diethylether.

The reaction temperatures in steps (1), (2), and (3) of Method III aregenerally in the range of from about -100° C. to about 150° C.,preferably from about -100° C. to about 125° C., and more preferablyfrom -100° C. to about 100° C.

The inventive metallocenes are transition metal-containing trihalocomplexes represented by the formula ZAMX₃ wherein Z is acyclopentadienyl-type group as described above, A is as described above,M is a Group IVB or VB transition metal, preferably titanium, zirconium,hafnium or vanadium, more preferably zirconium or titanium, mostpreferably zirconium, and X is a halide, preferably X is chlorine.

The metallocenes are prepared by reacting an alkali metal alkyl asdescribed above, the cyclopentadienyl-type ligand, and a metal halidecompound represented by the formula MX₄, wherein M is a transition metalas described above, and X is a halide.

Examples of suitable metal halides include titanium tetrachloride,titanium tetraiodide, titanium tetrabromide, zirconium tetrachloride,zirconium tetraiodide, zirconium tetrabromide, hafnium tetrachloride,hafnium tetraiodide, hafnium tetrabromide, vanadium tetrachloride,vanadium tetraiodide, vanadium tetrabromide, and mixtures thereof.Excellent results have been obtained with titanium tetrachloride andzirconium tetrachloride and they are preferred.

The alkali metal alkyl is selected from the alkyls of sodium, potassium,and lithium and the alkyl group would have 1 to 8, preferably 1 to 6carbon atoms. The preferred alkali metal alkyls are lithium alkyls. Dueto availability and efficacy, butyllithium is especially preferred.

The relative amounts of the alkali metal alkyl, thecyclopentadienyl-type ligand, and the metal halide can vary broadlydepending on the particular compounds employed. Generally the alkalimetal alkyl is present in an amount in the range of from about 0.5 moleto about 2.0 moles per mole of cyclopentadienyl-type ligand, preferablyin the range of from 0.5 mole to 1.75 moles, and more preferably from0.5 mole to 1.5 moles per mole of cyclopentadienyl-type ligand.Generally the metal halide will be present in an amount in the range offrom about 0.1 mole to about 50 moles per mole of cyclopentadienyl-typeligand, preferably in the range of from 0.2 mole to 20 moles, and morepreferably from 0.5 mole to 10 moles per mole of cyclopentadienyl-typeligand.

Generally a diluent is employed when reacting the alkali metal alkyl,the cyclopentadienyl-type ligand, and the metal halide to form themetallocene. Typical diluents include polar diluents such as for exampletetrahydrofuran, or nonpolar diluents such as alkanes, cycloalkanes,aromatic hydrocarbons, and non-cyclic ethers. Some specific examplesinclude benzene, toluene, heptane, cyclohexane, hexane, anddiethylether.

The temperature for reacting the alkali metal alkyl, thecyclopentadienyl-type ligand, and the metal halide is generally in therange of from about -100° C. to about 100° C., preferably from about-100° C. to about 80° C., and more preferably from -100° C. to 60° C.Although the alkali metal alkyl, the cyclopentadienyl-type ligand, andthe metal halide can be added in any order, it is preferred to firstreact the alkali metal alkyl with the cyclopentadienyl-type ligand toproduce an alkali metal salt of the cyclopentadienyl-type ligand, andthen react the alkali metal salt of the cyclopentadienyl-type ligandwith the metal halide.

Typical examples of the inventive metallocenes include

[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,

[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,

[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtribromide,

[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtribromide,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtribromide,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtribromide,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtribromide,

[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtribromide,

[1-phenyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenylzirconiumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]indenylzirconium trichloride,

9-(1-(2-dimethylphosphino)ethyl)fluorenylzirconium trichloride,

[(dimethylamino)methyl)]cyclopentadienylzirconium trichloride,

[(diethylamino)methyl)]cyclopentadienylzirconium trichloride,

[(dimethylamino)(phenyl)methyl)]cyclopentadienylzirconium trichloride,

[(diethylamino)(phenyl)methyl)]cyclopentadienylzirconium trichloride,

[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienylzirconiumtrichloride,

[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienylzirconiumtrichloride,

[1-phenyl-2-(dimethylamino)ethyl]cyclopentadienylzirconium trichloride,

[1-phenyl-2-(diethylamino)ethyl)cyclopentadienylzirconium trichloride,

[1-phenyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,

[1,1-dimethyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,

[1,1-diphenyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,

[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,

[1-tert-butyl-2-(dimethylamino)ethyl]indenylzirconium trichloride,

9-(1-(2-dimethylamino)ethyl)fluorenylzirconium trichloride,

[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,

[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,

[1-phenyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenyltitaniumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]indenyltitanium trichloride,9-(1-(2-dimethylphosphino)ethyl)fluorenyltitanium trichloride,

[(dimethylamino)methyl)]cyclopentadienyltitanium trichloride,

[(diethylamino)methyl)]cyclopentadienyltitanium trichloride,

[(dimethylamino)(phenyl)methyl)]cyclopentadienyltitanium trichloride,

[(diethylamino)(phenyl)methyl)]cyclopentadienyltitanium trichloride,

[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienyltitaniumtrichloride,[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienyltitaniumtrichloride,

[1-phenyl-2-(diethylamino)ethyl]cyclopentadienyltitanium trichloride,

[1-phenyl-2-(dimethylamino)ethyl)cyclopentadienyltitanium trichloride,

[1-phenyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,

[1,1-dimethyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,

[1,1-diphenyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,

[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,

[1-tert-butyl-2-(dimethylamino)ethyl]indenyltitanium trichloride,

9-(1-(2-dimethylamino)ethyl)fluorenyltitanium trichloride,

[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadiumtrichloride,

[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadiumtrichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadiumtrichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadiumtrichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadiumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylvanadiumtrichloride,

[1-phenyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenylvanadiumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]indenylvanadium trichloride,

9-(1-(2-dimethylphosphino)ethyl)fluorenylvanadium trichloride,

[(dimethylamino)methyl)]cyclopentadienylvanadium trichloride,

[(diethylamino)methyl)]cyclopentadienylvanadium trichloride,

[(dimethylamino)(phenyl)methyl)]cyclopentadienylvanadium trichloride,

[(diethylamino)(phenyl)methyl)]cyclopentadienylvanadium trichloride,

[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienylvanadiumtrichloride,

[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienylvanadiumtrichloride,

[1-phenyl-2-(diethylamino)ethyl]cyclopentadienylvanadium trichloride,

[1-phenyl-2-(dimethylamino)ethyl)cyclopentadienylvanadium trichloride,

[1-phenyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,

[1,1-dimethyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,

[1,1-diphenyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,

[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,

[1-tert-butyl-2-(dimethylamino)ethyl]indenylvanadium trichloride,

9-(1-(2-dimethylamino)ethyl)fluorenylvanadium trichloride,

[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafniumtrichloride,

[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafniumtrichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafniumtrichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafniumtrichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafniumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylhafniumtrichloride,

[1-phenyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,

[1,1-dimethyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,

[1,1-diphenyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,

[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]indenylhafniumtrichloride,

[1-tert-butyl-2-(dimethylphosphino)ethyl]indenylhafnium trichloride,

9-(1-(2-dimethylphosphino)ethyl)fluorenylhafnium trichloride,

[(dimethylamino)methyl)]cyclopentadienylhafnium trichloride,

[(diethylamino)methyl)]cyclopentadienylhafnium trichloride,

[(dimethylamino)(phenyl)methyl)]cyclopentadienylhafnium trichloride,

[(diethylamino)(phenyl)methyl)]cyclopentadienylhafnium trichloride,

[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienylhafniumtrichloride,

[(diethylamino)(methyl)(phenyl)methyl)]cyclopentadienylhafniumtrichloride,

[1-phenyl-2-(diethylamino)ethyl]cyclopentadienylhafnium trichloride,

[1-phenyl-2-(dimethylamino)ethyl)cyclopentadienylhafnium trichloride,

[1-phenyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,

[1,1-dimethyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,

[1,1-diphenyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,

[1-methyl-1-phenyl-2-(dimethylamino)ethyl]indenylhafnium trichloride,

[1-tert-butyl-2-(dimethylamino)ethyl]indenylhafnium trichloride, and

9-(1-(2-dimethylamino)ethyl)fluorenylhafnium trichloride.

The metallocenes can be used in combination with a suitable cocatalystto produce catalyst systems for the polymerization of olefins. Examplesof suitable cocatalysts include any of those organometallic cocatalystswhich have in the past been employed in conjunction with transitionmetal-containing olefin polymerization catalysts. Some typical examplesinclude organometallic compounds of metals of Groups IA, IIA, and IIIBof the Periodic Table. Examples of such compounds include organometallichalide compounds, organometallic hydrides, and metal hydrides. Somespecific examples include triethylaluminum, tri-isobutylaluminum,diethylaluminum chloride, diethylaluminum hydride, and the like. Otherexamples of known cocatalysts include the use of a stablenon-coordinating counter anion such as disclosed in U.S. Pat. No.5,155,080, e.g. using triphenyl carbeniumtetrakis(pentafluorophenyl)boronate. Another example would be the use ofa mixture of trimethylaluminum and dimethylfluoroaluminum such asdisclosed by Zambelli et, Macromolecules, 22, 2186 (1989).

Currently, organoaluminoxane cocatalysts are the preferred cocatalysts.Various techniques are known for making organoaluminoxanes. Onetechnique involves the controlled addition of water to atrialkylaluminum. Another technique involves combining atrialkylaluminum and a hydrocarbon with a compound containing water ofadsorption or a salt containing water of crystallization. Many suitableorganoaluminoxanes are commercially available.

Typically the organoaluminoxanes comprise oligomeric, linear and/orcyclic hydrocarbyl aluminoxanes having repeating units of the formula##STR2## wherein each R² is a hydrocarbyl group, preferably an alkylgroup containing 1-8 carbon atoms, x is 2 to 50, preferably 4 to 40, andmore preferably 10 to 40. Typically R² is predominantly methyl or ethyl.Preferably at least about 30 mole percent of the repeating groups havean R² which is methyl, more preferably at least 50 mole percent, andstill more preferably at least 70 mole percent. Generally in thepreparation of an organoaluminoxane, a mixture of linear and cycliccompounds is obtained. Organoaluminoxanes are commercially available inthe form of hydrocarbon solutions, generally aromatic hydrocarbonsolutions.

A solid organoaluminoxy product can be prepared by reacting anorganoaluminoxane and an oxygen-containing compound selected from thegroup consisting of organo boroxines, organic boranes, organicperoxides, alkylene oxides, and organic carbonates.

The amount of organoaluminoxane relative to the metallocene can varybroadly depending upon the particular catalyst selected and the resultsdesired. Typically, the organoaluminoxane is present in the amount ofabout 0.5 moles to about 10,000 moles aluminum per mole of metal in themetallocene, preferably about 10 moles to about 5,000 moles, and morepreferably 50 moles to 5,000 moles.

The above described steps for preparing the catalyst system aregenerally conducted in the presence of a solvent or a diluent. Typicalsolvents or diluents include for example tetrahydrofuran, heptane,hexane, cyclohexane, benzene, toluene, and diethylether.

A variety of olefin compounds are suitable for use as monomers in thepolymerization process of the present invention. Olefins which can beemployed include linear, branched, and cyclic aliphatic olefins. Whilethe invention would appear to be suitable for use with any aliphaticolefin known to be employed with metallocenes, those olefins having 2 to18 carbon atoms are most often used. Ethylene and propylene areespecially preferred. Often a second olefin (comonomer) having from 2 to12 carbon atoms, preferably from 4 to 10 carbon atoms can be employed.Typical comonomers include propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 2-pentene, 1-hexene, 2-hexene, cyclohexene,1-heptene, and dienes such as butadiene.

The polymerization processes according to the present invention can beperformed either batchwise or continuously. The olefin, metallocene, andorganoaluminoxane cocatalyst can be contacted in any order. It ispreferred that the metallocene and the organoaluminoxane are contactedprior to contacting with the olefin. Generally a diluent such asisobutane is added to the reactor. The reactor is heated to the desiredreaction temperature and olefin, such as ethylene, is then admitted andmaintained at a partial pressure within a range of from about 0.5 MPa toabout 5.0 MPa (70-725 psi) for best results. At the end of thedesignated reaction period, the polymerization reaction is terminatedand the unreacted olefin and diluent vented. The reactor can be openedand the polymer can be collected as a free-flowing white solid and driedto obtain the product.

The reaction conditions for contacting the olefin and the catalystsystem can vary broadly depending on the olefin employed, and are thosesufficient to polymerize the olefins. Generally the temperature is inthe range of about 20° C. to about 300° C., preferably in the range of50° C. to 150° C. The pressure is generally in the range of from about0.5 MPa to about 5.0 MPa (70-725 psi).

The present invention can be employed in any olefin polymerizationprocess known such as gas phase particle form, slurry type, or solutionphase polymerizations. A preferred type particle form polymerizationinvolves a continuous loop reactor which is continuously charged withsuitable quantities of diluent, catalyst system, and polymerizablecompounds in any desirable order. Typically the polymerization willinclude a higher alpha-olefin comonomer and optionally hydrogen.Generally the particle form polymerization is conducted at a temperaturein the range of about 50° C. to about 110° C., although higher and lowertemperatures can be used. Polyethylenes of varying molecular weightdistribution can be produced by varying the amount of hydrogen. Thereaction mixture containing polymer can be continuously withdrawn andthe polymer recovered as appropriate, generally by flashing the diluentand unreacted monomers and drying the resulting polymer.

The following examples serve to show the present invention in detail byway of illustration and not by way of limitation.

EXAMPLES

The examples demonstrate the effectiveness of the inventive processes inpreparing new cyclopentadienyl-type ligands and metallocene compoundsand the use of such metallocene compounds in catalyst systems.

Example 1 Cyclopentadienyl-type Ligands

Cyclopentadienyl-type ligands were prepared employing Method I byreacting 19 mmol LiCH₂ P(CH₃)₂ dissolved in 70 mL tetrahydrofuran (THF)with 19 mmol fulvene compound dissolved in 25 mL THF at 0° C. Thefulvene solution was added dropwise over a period of 30 to 90 minutes.The reaction mixture was stirred for 90 minutes at 0° C. The solvent wasremoved under vacuum and the residue was hydrolyzed with aqueous NH₄ Clsolution and extracted with 2×30 mL pentane. The extract was filteredover anhydrous Na₂ SO₄ and dried under vacuum. The fulvene compoundsemployed, the resulting cyclopentadienyl-type ligands, and therespective yields are indicated below:

6-phenylfulvene was employed in preparing

[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadiene and produced 72.9%yield of orange oil;

6,6-dimethylfulvene was employed in preparing

[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadiene and produced ayield of 36.0 % as a yellow oil;

6,6-diphenylfulvene was employed in preparing

[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadiene which yielded35.0% as an orange oil; and

6-tert-butylfulvene was employed in preparing

[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadiene and produced a63.2% yield as an orange oil.

Example 2 Metallocenes

Metallocene compounds were prepared by reacting thecyclopentadienyl-type ligands with metal halides. In a typical example,1.60 g (5.28 mmol)[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadiene, prepared asdescribed in Example 1, dissolved in 60 mL hexane was reacted with 3.30mL (5.28 mmol) n-BuLi (1,6M in hexane). The n-BuLi was added dropwiseover a period of 30 minutes at room temperature. The reaction mixturecontaining orange precipitate was stirred until the evolution of butanegas ceased. The reaction mixture was cooled to -20° C. employing anisopropyl alcohol-dry ice bath and then 0.87 mL (7.92 mmol) anhydrousTiCl₄ was added dropwise over 20 minutes. The mixture was stirred for 2hours at -20° C. The resulting brown suspension was filtered and washedwith 20 mL of hexane. The filtrate was concentrated under vacuum andplaced in a refrigerator. A yellow-green precipitate separated from themother liquor (solid I). The brown solid obtained by filtration waswashed with large amounts of toluene and CH₂ Cl₂. The resulting solutionwas dried to give a yellow solid (solid II). Solids I and II werecombined to give 0.81 g (1.76 mmol)[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride for an overall yield of 33.3%. The metallocene compounds[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,and [1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride were prepared in a similar fashion employing the respectivecyclopentadienyl-type ligands.

Example 3

A cyclopentadienyl-type ligand containing fluorene was prepared asfollows employing Method II. To a solution of 1.2 g LiCH₂ P(CH₃)₂ in 50mL THF was added 3.0 g (bromomethyl)fluorene in 50 mL THF at -78° C.over a period of one hour. The mixture was stirred an additional 30minutes at room temperature. Filtration of the mixture gave a clearyellow solution.

A fluorene-containing metallocene was prepared by reacting the thusprepared yellow solution with 7.1 mL n-butyllithium (1.5M in hexane).After stirring for 2 hours at room temperature the solvent was removedand then 30 mL ether was added. Then a solution of 2.5 g ZrCl₄ in 10 mLether was added at -78° C. The mixture was stirred for 10 minutes at-78° C. and one hour at room temperature. Then the ether was removed and60 mL hexane was added. The hexane solution was filtered over Na₂ SO₄.The solvent was removed and the residue was extracted with 25 mL tolueneand the metallocene was crystallized at -78° C.

Example 4

A cyclopentadienyl-type ligand containing fluorene was prepared asfollows employing Method III. In a reaction vessel 8.3 g (0.05 mol)fluorene in 150 mL ether was reacted with 31.3 ml (0.05 mol)butyllithium (1.5M in hexane) and then with 6.3 mL (0.05 mol) SiMe₃ Clin 50 mL pentane to form trimethylsilylfluorene. Then 6.8 g (0.03 mol)of the thus produced trimethylsilylfluorene was reacted with 18.7 mL(0.03 mol) butyllithium (1.6M in hexane) and 8.12 mL (0.13 mol) CH₂ Cl₂in 100 mL pentane for two hours at room temperature to form (Me₃Si)(ClCH₂)Flu, where Me is methyl and Flu is fluorene. The solvent wasremoved leaving a yellow residue. Then 2.5 g (0.009 mol) (Me₃Si)(ClCH₂)Flu in 30 mL THF was reacted with 0.71 g (0.009 mol) LiCH₂PMe₂ in 50 mL THF with stirring at -78° C. to form Me₃ Si)(Me₂P(CH₂)₂)Flu. The (Me₃ Si)(ClCH₂)Flu was added over a period of two hoursand the reaction was allowed to continue an additional three hours at-78° C. and then overnight at room temperature. The solvent was removedand the hexane gave 1.35 g of dark yellow oily product.

The fluorene-containing metallocene was prepared by reacting 1.35 g(0.004 mol) (Me₃ Si)(Me₂ P(CH₂)₂)Flu in 50 mL hexane with 3.5 mL (0,006mol) butyllithium (1.5M in hexane) and 1.1 g (0.004 mol) ZrCl₄ in 10 mLhexane. The ZrCl₄ was added over a period of 2 hours at -78° C. and thenstirred for an additional hour at 25° C. The reaction mixture wasfiltered over Na₂ SO₄. The solvent was removed and a yellow-brown finepowder was obtained

Example 5 Polymerizations

Several catalyst systems were employed in the polymerization ofethylene. The conditions included a total pressure of 450 psig, apartial pressure of H₂ of 10 psig, and a temperature of 90° C. Thepolymerization was conducted in 2 liters isobutane diluent for one hour.

The catalyst systems employed in Runs 101-104 were prepared bycontacting 10 mL MAO from Shering with 0.003-0.005 g of eachmetallocene. The metallocene[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride was employed in Runs 101 and 102. The metallocene[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride was employed in Runs 103 and 104. The polymerizations inRuns 101-104 were conducted employing 3.0 mL of each catalyst system.

The catalyst system in Run 105 was prepared by contacting 9.38 mL MAOfrom Ethyl, 0.62 mL toluene and 0.0123 g of the metallocene[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride.

The results are tabulated in the Table below. A1/M is the molesaluminum/mole transition metal employed. Methylaluminoxane was employedas the cocatalyst. Hexene is the grams hexene-1 employed as comonomer.Productivity is the g polyethylene/g transition metal•hour. MI is themelt index in g/10 min. run according to ASTM 1238. Density is g/ccmeasured according to ASTM 1505.

                  TABLE                                                           ______________________________________                                                                     Productivity                                                            Hexene                                                                              g PE/g  MI g/10                                                                             Density                            Run  Metallocene                                                                             A1/M    grams M · hr                                                                       min.  g/cc                               ______________________________________                                        101  A*        730     0     19,000  0.001 0.9714                             102  A*        730     50    13,000  0     0.9791                             103  B*        1000    0     8,000   0     0.9653                             104  B*        1000    50    6,500   0     0.9763                             105  C*        470     0     364,000 1.91  0.9688                             ______________________________________                                         *A is [1,1dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium        trichloride                                                                   *B is [1,1diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitanium        trichloride                                                                   *C is [1,1dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconium       trichloride                                                              

That which is claimed is:
 1. A compound represented by the formula ZAMX₃:wherein Z is a cyclopentadienyl-type group and is an unsubstitutedcyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl,substituted indenyl, unsubstituted fluorenyl, or substituted fluorenylgroup, wherein the substituents on said cyclopentadienyl-type group arehydrocarbyl groups containing 1 to 12 carbon atoms, alkoxy groupscontaining 1 to 12 carbon atoms, trialkylsilyl groups where each alkylgroup contains 1 to 12 carbon atoms, alkyl halide groups where the alkylgroup contain 1 to 12 carbon atoms, or halide; wherein A is --YPR₂,--YNR₂, or --NR₂, wherein Y is an alkylene group containing 1to 24carbon atoms, wherein each R is individually selected from alkyl groupscontaining 1to 20 carbon atoms; wherein M is a Group IVB or VBtransition metal; and wherein X is a halide.
 2. A compound according toclaim 1, wherein M is titanium or zirconium.
 3. A compound according toclaim 1 whichis[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,[1,1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride,[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienylzirconiumtrichloride, 9-(1-(2-dimethylphosphino)ethyl)fluorenylzirconiumtrichloride,[1-methyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,[1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,[1,1-dimethyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride, [1.1-diphenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,[1-methyl-1-phenyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride,[1-tert-butyl-2-(dimethylphosphino)ethyl]cyclopentadienyltitaniumtrichloride, or 9-(1-(2-dimethylphosphino)ethyl)fluorenyltitaniumtrichloride.
 4. A compound according to claim 1 whichis[(dimethylamino)methyl)]cyclopentadienylzirconium trichloride,[(dimethylamino)(phenyl)methyl)]cyclopentadienylzirconium trichloride,[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienylzirconiumtrichloride, [1-phenyl-2-(dimethylamino)ethyl)cyclopentadienylzirconiumtrichloride, 9-(dimethylamino)methyl)fluorenylzirconium trichloride,9-(1-(2-dimethylamino)ethyl)fluorenylzirconium trichloride,[(dimethylamino)methyl)]cyclopentadienyltitanium trichloride,[(dimethylamino)(phenyl)methyl)]cyclopentadienyltitanium trichloride,[(dimethylamino)(methyl)(phenyl)methyl)]cyclopentadienyltitaniumtrichloride, [1-phenyl-2-(dimethylamino)ethyl)cyclopentadienyltitaniumtrichloride, 9-(dimethylamino)methyl)fluorenyltitanium trichloride, or9-(1-(2-dimethylamino)ethyl)fluorenyltitanium trichloride.
 5. A compoundaccording to claim 1 wherein Y contains 1 to 20 carbon atoms and whereineach R contains 1 to 10 carbon atoms.
 6. A compound according to claim 5wherein Y contains 1 to 16 carbon atoms and wherein each R contains 1 to5 carbon atoms.
 7. A compound according to claim 6 wherein Y is anunsubstituted or substituted methylene or ethylene group and whereineach R is methyl.
 8. A compound according to claim 7 wherein thesubstituents on said cyclopentadienyl-type group are alkyl groupscontaining 1 to 10 carbon atoms.
 9. A compound according to claim 8wherein the substituents are alkyl groups containing 1 to 6 carbonatoms.
 10. A compound according to claim 9 wherein A is --CH₂ P(CH₃)₂.